Blends of polyarylether sulphone and polyamide, with improved viscosity and flowability

ABSTRACT

The thermoplastic molding composition comprises components A, C, D, E and, where appropriate, B, F and G, the total weight of which is 100% by weight, and also component H:  
     a) as component A, from 5 to 94.8% by weight of at least one polyaryl ether sulfone,  
     b) as component B, from 0 to 20% by weight of at least one functionalized polyaryl ether sulfone,  
     c) as component C, from 5 to 94.8% by weight of at least one polyamide,  
     d) as component D, from 0.1 to 10% by weight of at least one epoxy resin,  
     e) as component E, from 0.1 to 60% by weight of fibrous or particulate fillers or a mixture of these,  
     f) as component F, from 0 to 40% by weight of impact-modifying rubbers which have functional groups,  
     g) as component G, from 0 to 40% by weight of other conventional additives and processing aids,  
     h) as component H, from 100 ppm to 0.5% by weight, based on the amounts of components A to G, of copper bromide and/or copper iodide.

[0001] The present invention relates to polyaryl ether sulfone/polyamideblends with improved toughness and flowability, to a process for theirproduction, and to their use. Blends made from polyaryl ether sulfoneswith polyamides are known per se. By way of example, DE-A-21 22 735describes thermoplastic polymer mixtures made from aromatic polysulfoneswith polyamides. Products of this type have advantageous properties,such as high stiffness and good chemical resistance. A disadvantage isthe low toughness of these materials, attributable to the chemicalincompatibility of the components. In addition, flowability is notadequate for every application, especially in the case of injectionmolding.

[0002] EP-A-0 477 757 also describes polyamide/polyaryl ether sulfoneblends which have partly aromatic polyamides. The molding compositionsdescribed have improved stiffness and strength at up to 110° C.

[0003] The molding compositions known hitherto do not have adequate heatresistance for every application. If the products are used for prolongedperiods above 150° C., their level of mechanical properties deterioratesmarkedly.

[0004] Molding compositions with improved heat resistance are describedin the earlier-priority unpublished document DE-A-198 39 331. However,the toughness and flowability of these products is still inadequate forsome applications.

[0005] It is an object of the present invention to provide polyarylether sulfone/polyamide blends which have improved toughness andflowability in addition to good heat resistance.

[0006] We have found that this object is achieved by means of athermoplastic molding composition comprising components A, C, D, E and,where appropriate, B, F and G, the total weight of which is 100% byweight, and also component H:

[0007] a) as component A, from 5 to 94.8% by weight of at least onepolyaryl ether sulfone,

[0008] b) as component B, from 0 to 20% by weight of at least onefunctionalized polyaryl ether sulfone,

[0009] c) as component C, from 5 to 94.8% by weight of at least onepolyamide,

[0010] d) as component D, from 0.1 to 10% by weight of at least oneepoxy resin,

[0011] e) as component E, from 0.1 to 60% by weight of fibrous orparticulate fillers or a mixture of these,

[0012] f) as component F, from 0 to 40% by weight of impact-modifyingrubbers which have functional groups,

[0013] g) as component G, from 0 to 40% by weight of other conventionaladditives and processing aids,

[0014] h) as component H, from 100 ppm to 0.5% by weight, based on theamounts of components A to G, of copper bromide and/or copper iodide.

[0015] According to the invention, it has been found that the use inparticular of the epoxy resin described in component D markedly improvesthe impact strength and flowability of the polymer blends, while theother advantageous mechanical properties are retained.

[0016] The individual components of the thermoplastic moldingcompositions of the invention are described in more detail below.

[0017] Component A

[0018] The proportion of component A in the molding compositions of theinvention may vary over a wide range, from 5 to 94.8% by weight.Preferred molding compositions of the invention comprise from 15 to 85%by weight, in particular from 30 to 60% by weight, of component A, basedon the total weight of components A to G. Particularly preferred moldingcompositions comprise from 40 to 50% by weight of component A, based onthe total weight of A to G.

[0019] According to the invention, a polyarylene ether sulfone is usedas component A. It is also possible for a mixture of two or moredifferent polyarylene ether sulfones to be used as component A.

[0020] The arylene groups of the polyarylene ether sulfones A may beidentical or different and, independently of one another, are anaromatic radical having from 6 to 18 carbon atoms. Examples of suitablearylene radicals are phenylene, bisphenylene, terphenylene,1,5-naphthylene, 1,6-naphthylene, 1,5-anthrylene, 9,10-anthrylene and2,6-anthrylene. Among these, preference is given to 1,4-phenylene and4,4′-biphenylene. These aromatic radicals are preferably unsubstituted.However, they may have one or more substituents. Examples of suitablesubstituents are alkyl, arylalkyl, aryl, nitro, cyano and alkoxy groups,and also heteroaromatics, such as pyridine, and halogen. Preferredsubstituents include alkyl having up to 10 carbon atoms, such as methyl,ethyl, isopropyl, n-hexyl and isohexyl, C₁-C₁₀-alkoxy radicals, such asmethoxy, ethoxy, n-propoxy and n-butoxy, aryl radicals having up to 20carbon atoms, such as phenyl and naphthyl, and also fluorine andchlorine. Other preferred substituents are those obtainable by reactingthe polyarylene ether sulfones with a reactive compound which contains,besides a carbon-carbon double or triple bond, one or more carbonyl,carboxylic acid, carboxylate, anhydride, amide, imide, carboxylic ester,amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzylgroups. The bonding of the arylene groups to one another in thepolyarylene ethers may be via —SO₂—, or, for example, via —O—, —S—,—SO—, —CO—, —N═N—, —COO—, or via an unsubstituted or substitutedalkylene radical, or via a chemical bond.

[0021] Preferred polyarylene ether sulfones which may be used accordingto the invention (component A) have a structure made from repeat unitsof the formula I

[0022] where

[0023] t and q, independently of one another, are 0, 1, 2 or 3,

[0024] each of Q, T and Z, independently of one another, is a chemicalbond or a group selected from the class consisting of —O—, —S—, —SO₂—,S═O, C═O, —N═N—, —R^(a)C═CR^(b)— and —CR^(c)R^(d)—, where

[0025] each of R^(a) and R^(b), independently of one another, ishydrogen or C₁-C₁₂-alkyl and each of R^(c) and R^(d), independently ofone another, is hydrogen or C₁-C₁₂-alkyl, C₁-C₁₂-alkoxy or C₆-C₁₈-aryl,where

[0026] R^(c) and R^(d) may, if desired, independently of one anotherhave fluorine and/or chlorine substituents or, together with the carbonatom to which they are bonded, may form a C₃-C₁₂-cycloalkyl group, whichmay be unsubstituted or substituted by one or more C₁-C₆-alkyl groups,with the proviso that at least one of the groups T, Q and Z is —SO₂— orC═O and if t and q are 0, Z is —SO₂—, and

[0027] Ar and Ar¹, independently of one another, are C₆-C₁₈-arylene,unsubstituted or substituted by C₁-C₁₂-alkyl, C₆-C₁₈-aryl, C₁-C₁₂-alkoxyor halogen.

[0028] It is also possible for different units of the formula I to bepresent in the polyarylene ether sulfone, distributed randomly or inblocks.

[0029] One way of preparing polyarylene ethers A which may be usedaccording to the invention is a method based on GB 1 152 035 and U.S.Pat. No. 4,870,153. Examples of suitable process conditions for thesynthesis of polyarylene ether sulfones are described in EP-A-0 113 112and EP-A-0 135 130. The reaction of the monomers in aprotic polarsolvents in the presence of anhydrous alkali metal carbonate isparticularly suitable. A particularly preferred combination isN-methylpyrrolidone as solvent and potassium carbonate as catalyst. Thereaction in the melt is also preferred. However, the introduction ofterminal anhydride groups, as they are described, is not an essentialrequirement for the present invention. Examples of suitable polyaryleneether sulfones A are those having at least one of the following repeatstructural units I₁ to I₁₅:

[0030] Particularly preferred units of the formula I are those of theformulae I₁ and I₂, which may be present individually or in a mixture.

[0031] Component B

[0032] The amount of component B present in the molding compositions ofthe invention is preferably from 0 to 15% by weight, particularlypreferably from 0 (or if present, from 1) to 10% by weight.Functionalized polyaryl ether sulfones are used as component B.

[0033] The expressions “functionalized” and “having functional groups”,as used in the description and in the claims, relate to the presence offunctional groups which are suitable for chemical reaction withfunctional groups present in polyamides. In particular, these arefunctional groups capable of reaction with carboxyl groups or with aminogroups. Examples of functional groups of this type are hydroxyl, amino,anhydride, epoxy and carboxyl groups.

[0034] In one embodiment, the preferred functionalized polyarylene ethersulfones include, particularly in mixtures with polyarylene ethersulfones which contain inert groups, carboxyl-containing polyaryleneether sulfones with repeat structural units of the formulae I and II

[0035] where the variables are as defined above, Y is as defined for T,Q and Z, and Ar² and Ar³ are as defined for Ar and Ar¹, and R^(e) is H,C₁-C₆-alkyl or —(CH₂)_(n)—COOH, where n is a number from 0 to 10.

[0036] Examples of ways of obtaining these carboxyl-containingpolyarylene ethers are a method based on EP-A-0 185 237, and also theprocesses described by I. W. Parsons et al., in Polymer, 34, 2836 (1993)and T. Koch, H. Ritter, in Macromol. Phys. 195, 1709 (1994).

[0037] Examples of suitable structural units II are:

[0038] where in each case n is an integer from 0 to 4.

[0039] The polyarylene ether sulfones containing acid groups haveviscosity numbers of from about 15 to 80 ml/g (determined in 1% strengthNMP solution at 25° C.). If these polyarylene ether sulfones containingacid groups are used, the proportion of free acid groups in component Ais preferably from 0.05 to 25 mol %, with preference from 0.1 to 20 mol%, and particularly from 0.1 to 15 mol %, the proportion of acid groupsbeing determined by ¹H NMR, as in I. W. Parsons et al., Polymer, 34,2836 (1993).

[0040] The polyarylene ether sulfones A and B may also be copolymers orblock copolymers, in which there are polyarylene ether sulfone segmentsand segments of other thermoplastic polymers, such as polyesters,aromatic polycarbonates, polyester carbonates, polysiloxanes, polyimidesor polyetherimides. The molar masses (number average) of the blocks orof the graft branches in the copolymers are generally from 1000 to30,000 g/mol.

[0041] The blocks of different structure may have an alternating orrandom arrangement. The proportion by weight of the polyarylene ethersulfones in the copolymers or block copolymers is generally at least 10%by weight. The proportion by weight of the polyarylene ether sulfonesmay be up to 97% by weight. Preference is given to copolymers or blockcopolymers with a proportion of up to 90% by weight of polyarylene ethersulfones. Particular preference is given to copolymers or blockcopolymers having from 20 to 80% by weight of polyarylene ethersulfones.

[0042] The average molar masses M_(n) (number average) of thepolyarylene ether sulfones are generally from 5000 to 60,000 g/mol, andtheir relative viscosities are generally from 0.20 to 0.95 dl/g.Depending on the solubility of the polyarylene ether sulfones, therelative viscosities are measured either in 1% strength by weightN-methylpyrrolidone solution, in mixtures made from phenol anddichlorobenzene, or in 96% strength sulfuric acid, in each case at 20 or25° C.

[0043] Depending on the conditions for the synthesis, the polyaryleneether sulfones A and B may have various end groups. These include thosewhich are inert to component C and those which can react with functionalgroups of the polyamides C, in particular with the amino or carboxylgroups.

[0044] Inert end groups include halo, in particular chloro, alkoxy,particularly methoxy or ethoxy, aryloxy, preferably phenoxy, andbenzyloxy groups. Examples of reactive groups are hydroxyl, amino,anhydride, epoxy and carboxyl. Particular preference is given topolyarylene ether sulfones B having amino, anhydride or epoxy endgroups, or mixtures of these.

[0045] One way of preparing polyarylene ether sulfones B having hydroxylend groups is to select an appropriate molar ratio of dihydroxy anddichloro monomers (see, for example, McGrath et al., Polym. Eng. Sci.17, 647 (1977); Elias “Makromoleküle” 4th edn. (1981) pp. 490-493, Hütig& Wepf-Verlag, Basle).

[0046] One way of obtaining polyarylene ether sulfones B having aminoend groups is for compounds such as p-aminophenol to be present duringthe polymerization (J. E. McGrath, Polymer 30, 1552 (1989)).

[0047] An example of a description of the preparation of polyaryleneether sulfones B containing anhydride end groups is given in DE-A 44 29107.

[0048] Polyarylene ether sulfones B having epoxy end groups may beprepared from polyarylene ether sulfones having OH end groups, forexample by reacting the latter with suitable compounds which havepropylene oxide groups, or from which propylene oxide groups areobtainable, preferably epichlorohydrin.

[0049] The reaction of the hydroxyl-terminated polyarylene ethersulfones with epichlorohydrin preferably takes place at from 30 to 200°C., in a solvent. Examples of suitable solvents for this purpose arealiphatic or aromatic sulfides or sulfones, or else N-methylpyrrolidone.The reaction is generally carried out in a weakly basic medium in orderto prevent, as far as possible, ring-opening of the epoxy groups.

[0050] In one embodiment, the molding compositions of the inventioncomprise only polyarylene ether sulfones A which are substantially freefrom reactive end groups. However, it is also possible in a preferredembodiment to use mixtures of various polyarylene ether sulfones A and Bhaving inert and reactive end groups. An example of the proportion ofthe polyarylene ether sulfones having reactive end groups is from 2 to98% by weight, preferably from 5 to 50% by weight, based on components Aand B.

[0051] Component C

[0052] The amount of component C present in the molding compositions ofthe invention is from 5 to 94.8% by weight, preferably from 10 to 80% byweight, particularly from 10 to 50% by weight and specifically from 15to 25% by weight. This material is at least one polyamide. The polyamidehere may be freely selected from polyamides and copolyamides. Thematerials are thermoplastic polyamides.

[0053] The polyamides present as component C in the compositions arelikewise known and embrace semicrystalline and amorphous resins with amolecular weight (weight average) of at least 5000, these usually beingtermed nylon. Polyamides of this type are described in U.S. Pat. Nos.2,071,250; 2,071,251; 2,130,523; 2,130,948; 2,241,322; 2,312,966;2,512,606 and 3,393,210, for example.

[0054] One way of preparing the polyamides C is to condense equimolaramounts of a saturated or of an aromatic dicarboxylic acid having from 4to 12 carbon atoms with a saturated or aromatic diamine which has up to14 carbon atoms, or to condense ω-aminocarboxylic acids, or to carry outpolyaddition of appropriate lactams.

[0055] Examples of polyamides of this type arepolyhexamethyleneadipamide (nylon-6,6), polyhexamethyleneazelamide(nylon-6,9), polyhexamethylenesebacamide (nylon-6,10),polyhexamethylenedodecandiamide (nylon-6,12), the polyamides obtained byring-opening of lactams, for example polycaprolactam andpolylaurolactam, and also poly-11-aminoundecanoic acid, and a polyamidemade from di(p-aminocyclohexyl)methane and dodecanedioic acid.

[0056] It is also possible to use polyamides prepared bycopolycondensing two or more of the abovementioned monomers or theircomponents, e.g. copolymers made from adipic acid, isophthalic acid orterephthalic acid and hexamethylenediamine, or copolymers made fromcaprolactam, terephthalic acid and hexamethylenediamine. Partly aromaticcopolyamides of this type contain from 40 to 90% by weight of unitswhich derive from terephthalic acid and hexamethylenediamine. A smallproportion of the terephthalic acid, preferably not more than 10% byweight of the total of aromatic dicarboxylic acids used, may be replacedby isophthalic acid or by other aromatic dicarboxylic acids, preferablythose in which the carboxyl groups are in para position.

[0057] Other monomers which may be used are cyclic diamines, such asthose of the formula III

[0058] where

[0059] R^(f) is hydrogen or C₁-C₄-alkyl,

[0060] R^(g) is C₁-C₄-alkyl or hydrogen, and

[0061] R^(h) is C₁-C₄-alkyl or hydrogen.

[0062] Particularly preferred diamines III arebis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane,2,2-bis(4-aminocyclohexyl)propane, and2,2-bis(4-amino-3-methylcyclohexyl)propane.

[0063] Other diamines III which may be mentioned are 1,3- and1,4-cyclohexanediamine, and isophoronediamine.

[0064] Besides the units which derive from terephthalic acid andhexamethylenediamine, the partly aromatic copolyamides contain unitswhich derive from ε-caprolactam, and/or units which derive from adipicacid and hexamethylenediamine.

[0065] The proportion of units which derive from the ε-caprolactam is upto 50% by weight, preferably from 20 to 50% by weight, particularly from25 to 40% by weight, while the proportion of units which derive fromadipic acid and hexamethylenediamine is up to 60% by weight, preferablyfrom 30 to 60% by weight, and particularly from 35 to 55% by weight.

[0066] It is also possible for the copolyamides to contain both unitsderived from ε-caprolactam and units derived from adipic acid andhexamethylenediamine. In this case, care needs to be taken that theproportion of units free from aromatic groups is at least 10% by weight,preferably at least 20% by weight. There is no particular restrictionhere on the ratio of the units derived from ε-caprolactam and fromadipic acid and hexamethylenediamine.

[0067] Polyamides having from 50 to 80% by weight, particularly from 60to 75% by weight, of units derived from terephthalic acid andhexamethylenediamine, and from 20 to 50% by weight, preferably from 25to 40% by weight, of units which derive from ε-caprolactam have provento be particularly advantageous for many applications.

[0068] One way of preparing the partly aromatic copolyamides is theprocess described in EP-A-0 129 195 and EP-A-0 129 196.

[0069] Preferred partly aromatic polyamides are those whose content oftriamine units, in particular units of dihexamethylenetriamine, is below0.5% by weight. Particular preference is given to partly aromaticpolyamides of this type having triamine contents of 0.3% by weight orbelow.

[0070] Preference is given to linear polyamides with a melting pointabove 200° C.

[0071] Preferred polyamides are polyhexamethyleneadipamide,polyhexamethylenesebacamide and polycaprolactam, and also nylon-6/6,Tand nylon-6,6/6,T, and also polyamides which contain cyclic diamines ascomonomers. The polyamides generally have a relative viscosity of from2.0 to 5, determined on a 1% strength by weight solution in 96% strengthsulfuric acid at 23° C., corresponding to a molecular weight (numberaverage) of from about 15,000 to 45,000. It is particularly preferableto use polyamides with a relative viscosity of from 2.4 to 3.5, inparticular from 2.5 to 3.4.

[0072] Mention should also be made of polyamides obtainable, forexample, by condensing 1,4-diaminobutane with adipic acid at an elevatedtemperature (nylon-4,6). Preparation processes for polyamides of thisstructure are described in EP-A-0 038 094, EP-A-0 038 582 and EP-A-0 039524, for example.

[0073] Other suitable copolyamides C according to the invention areessentially composed of

[0074] c1: from 30 to 44 mol %, preferably from 32 to 40 mol %, andparticularly from 32 to 38 mol %, of units C₁ which derive fromterephthalic acid,

[0075] c2: from 6 to 20 mol %, preferably from 10 to 18 mol %, andparticularly from 12 to 18 mol %, of units C₂ which derive fromisophthalic acid,

[0076] c3: from 43 to 49.5 mol %, preferably from 46 to 48.5 mol %, andparticularly from 46.3 to 48.2 mol %, of units C₃ which derive fromhexamethylenediamine,

[0077] c4: from 0.5 to 7 mol %, preferably from 1.5 to 4 mol %, andparticularly from 1.8 to 3.7 mol %, of units C₄ which derive fromaliphatic cyclic diamines having from 6 to 30 carbon atoms, preferablyfrom 13 to 29 carbon atoms, and particularly from 13 to 17 carbon atoms,preferably having the abovementioned formula III, and

[0078] c5: from 0 to 4 mol % of polyamide-forming monomers C₅ other thanC₁-C₄,

[0079] where the molar percentages of components C₁ to C₅ give 100% intotal.

[0080] It is preferable for the amounts of the diamine units C₃ and C₄reacted with the dicarboxylic acid units C₁ and C₂ to be approximatelyequimolar.

[0081] Besides the units C₁ to C₄ described above, the copolyamides Cmay contain, based on components C₁ to C₄, up to 4% by weight,preferably up to 3.5% by weight, of other polyamide-forming monomers C₅.

[0082] Examples of aromatic dicarboxylic acids are substitutedterephthalic and isophthalic acids, such as 3-tert-butylisophthalicacid, polynuclear dicarboxylic acids, e.g. 4,4′- and3,3′-biphenyldicarboxylic acid, 4,4′- and3,3′-diphenylmethanedicarboxylic acid, 4,4′- and 3,3′-diphenyl sulfonedicarboxylic acid, 1,4- and 2,6-naphthalenedicarboxylic acid, andphenoxyterephthalic acid.

[0083] Examples of other polyamide-forming monomers C₅ may derive fromdicarboxylic acids having from 4 to 16 carbon atoms and from aliphaticdiamines having from 4 to 16 carbon atoms, or else from aminocarboxylicacids or, respectively, corresponding lactams having from 7 to 12 carbonatoms. Suitable monomers of these types which may be mentioned here,merely as examples, are suberic acid, azelaic acid and sebacic acid asrepresentatives of the aliphatic dicarboxylic acids, 1,4-butanediamine,1,5-pentanediamine and piperazine as representatives of the diamines,and caprolactam, capryllolactam, enantholactam, laurolactam andω-aminoundecanoic acid as representatives of lactams and aminocarboxylicacids.

[0084] The melting points of these copolyamides C are generally from 290to 340° C., preferably from 292 to 330° C., this melting point generallybeing associated with a high glass transition point, generally above120° C., particularly above 130° C. (in the dry state).

[0085] According to the invention, it is preferable to use polyamides Cwhose degree of crystallinity is >30%, preferably >35%, and particularly>40%.

[0086] The degree of crystallinity is a measure of the proportion ofcrystalline fragments in the copolyamide, and is determined by X-raydiffraction, or indirectly by measuring ΔH_(cryst).

[0087] It is, of course, also possible to use mixtures of thesecopolyamides C, with any desired mixing ratio.

[0088] Suitable processes for preparing the copolyamides are known tothe skilled worker (see also EP-A-0 702 058).

[0089] The viscosity number of the polyamides or copolyamides ofcomponent C used according to the invention, measured in 96% strengthsulfuric acid, 0.5% strength solution, in accordance with DIN 53 727, ispreferably above 140 ml/g, with preference above 150 ml/g.

[0090] Component D

[0091] As component D, the molding compositions of the inventioncomprise from 0.1 to 10% by weight, preferably from 0.3 to 8% by weight,particularly from 0.5 to 2% by weight, of at least one epoxy resin. Anyknown epoxy resin may be used here. A comprehensive description of epoxyresins may be found in B. Ellis (ed.), Chemistry and Technology of EpoxyResins, Blackie Academic & Professional 1993.

[0092] Preferred epoxy resins are those of the formula II, usuallyobtainable by condensing 2,2-bis(p-hydroxyphenyl)propane (bisphenol A)and epichlorohydrin.

[0093] They preferably have the formula II D below:

[0094] where

[0095] R¹ is hydrogen, or alkyl having from 1 to 16 carbon atoms,preferably methyl, and

[0096] n is from 2 to 50, preferably from 2 to 13.

[0097] The epoxy value to ISO 3001 of epoxy resins is usually from 1.5to 1.9, preferably from 1.68 to 1.75. Their softening point to DIN 51920is preferably from 75 to 100° C., and particularly from 82 to 90° C.Their melt viscosity to DIN 53018 Ti at 175° C. is preferably from 250to 600 mPas, particularly from 350 to 480 mPas.

[0098] Other preferred epoxy resins are those of the formula III D

[0099] where n is as defined for II D and R^(2′) is alkyl having from 1to 16 carbon atoms.

[0100] Preferred R^(2′) are propyl and butyl.

[0101] Other suitable epoxy resins have the formula IV D

[0102] where R^(3′) and n are as defined under formula II for R^(1′) andn, R^(3′) preferably being hydrogen.

[0103] Cycloaliphatic epoxy resins (formula V D) are also suitable:

[0104] where R^(4′) is alkyl having from 1 to 16 carbon atoms. Otherpreferred resins which should be mentioned are condensation products ofalcohols, particularly of diols and/or of bisphenols, with triglycidylisocyanurate.

[0105] It is preferable to use solid epoxy resins whose softening point,determined to DIN 51920, is above 60° C., preferably above 70° C.However, liquid or semi-solid resins may also be used.

[0106] Component E

[0107] The molding compositions of the invention comprise from 0.1 to60% by weight of fibrous or particulate fillers or mixtures of these. Itis preferable for the molding compositions of the invention to comprisefrom 4.7 to 50% by weight, and particularly from 1.5 to 40% by weight,of fibrous or particulate fillers (or reinforcing materials) or amixture of these.

[0108] Preferred fibrous fillers or fibrous reinforcing materials arecarbon fibers, potassium titanate whiskers, aramid fibers andparticularly glass fibers. If glass fibers are used they may have beenprovided with a size, preferably a polyurethane size, and with acoupling agent, to improve compatibility with the matrix material. Thecarbon fibers and glass fibers used generally have a diameter of from 6to 20 μm.

[0109] The glass fibers may be incorporated either as short glass fibersor else as continuous-filament strands (rovings). The average length ofthe glass fibers in the finished injection molding is preferably from0.08 to 0.5 mm.

[0110] Carbon fibers or glass fibers may also be used as wovens, mats orglass filament rovings.

[0111] Suitable particulate fillers are amorphous silica, carbonates,such as magnesium carbonate or chalk, powdered quartz, mica, a very widevariety of silicates, such as clays, muscovite, biotite, suzoite, tinmaletite, talc, chlorite, phlogophite, feldspar, calcium silicates, suchas wollastonite, or aluminum silicates, such as kaolin, particularlycalcined kaolin.

[0112] In one particularly preferred embodiment, use is made ofparticulate fillers in which at least 95% by weight, preferably at least98% by weight, of the particles have a diameter (maximum dimension),determined on the finished product, of less than 45 μm, preferably lessthan 40 μm, and an aspect ratio, determined on the finished product, offrom 1 to 25, preferably from 2 to 20.

[0113] One way of determining the particle diameters here is by takingelectron micrographs of cross sections of the polymer mixture and usingat least 25, preferably at least 50, filler particles for theevaluation. The particle diameters may also be determined bysedimentation analysis as in Transactions of ASAE, p. 491 (1983). Theproportion by weight of fillers below 40 μm may also be measured byscreen analysis. The aspect ratio is the ratio of particle diameter tothickness (largest to smallest dimension).

[0114] Particularly preferred particulate fillers are talc, kaolin, suchas calcined kaolin, and wollastonite, and mixtures of two or all ofthese fillers. Among these, particular preference is given to talc witha proportion of at least 95% by weight of particles of diameter lessthan 40 μm, and with an aspect ratio of from 1.5 to 25, determined ineach case on the finished product. Kaolin preferably has a proportion ofat least 95% by weight of particles of diameter less than 20 μm, andwith an aspect ratio of from 1.2 to 20, determined in each case on thefinished product.

[0115] Component F

[0116] The molding compositions of the invention may, if desired,comprise impact-modifying rubbers F, which have functional groups. Theirproportion may vary over a wide range. Preferred molding compositions ofthe invention comprise from 0 to 30% by weight, particularly from 0 to20% by weight, of component F, based on the total weight of A-G.Particularly preferred molding compositions comprise from 0 to 17.5% byweight of component F, based on the total weight of A to G.

[0117] Mixtures of two or more different impact-modifying rubbers mayalso be used as component F.

[0118] Rubbers which increase the toughness of molding compositionsgenerally have two significant features: they comprise an elastomericfraction which has a glass transition temperature below −10° C.,preferably below −30° C., and they contain at least one functional groupwhich can interact with the polyamide or polyaryl ether. Examples ofsuitable functional groups are carboxylic acid, carboxylic anhydride,carboxylic ester, carboxamide, carboximide, amino, hydroxyl, epoxy,urethane and oxazoline groups.

[0119] Preferred functionalized rubbers include functionalizedpolyolefin rubbers built up from the following components:

[0120] f₁) from 40 to 99% by weight of at least one α-olefin having from2 to 8 carbon atoms;

[0121] f₂) from 0 to 50% by weight of a diene;

[0122] f₃) from 0 to 45% by weight of a C₁-C₁₂-alkyl ester of acrylicacid or methacrylic acid, or mixtures of esters of this type;

[0123] f₄) from 0 to 40% by weight of an ethylenically unsaturatedC₂-C₂₀ mono- or dicarboxylic acid or of a functional derivative of anacid of this type;

[0124] f₅) from 1 to 40% by weight of a monomer containing epoxy groups;and

[0125] f₆) from 0 to 5% by weight of other monomers capable offree-radical polymerization.

[0126] Examples of suitable α-olefins f₁) are ethylene, propylene,1-butylene, 1-pentylene, 1-hexylene, 1-heptylene, 1-octylene,2-methylpropylene, 3-methyl-1-butylene and 3-ethyl-1-butylene. Ethyleneand propylene are preferred.

[0127] Examples of suitable diene monomers f₂) are conjugated dieneshaving from 4 to 8 carbon atoms, such as isoprene and butadiene,nonconjugated dienes having from 5 to 25 carbon atoms, such as1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadieneand 1,4-octadiene, cyclic dienes, such as cyclopentadiene,cyclohexadienes, cyclooctadienes and dicyclopentadiene, and alsoalkenylnorbornenes, such as 5-ethylidene-2-norbornene,5-butylidene-2-norbornene, 2-methallyl-5-norbornene and2-isopropenyl-5-norbornene, and tricyclodienes, such as3-methyltricyclo[5.2.1.0.2.6]-3,8-decadiene, or mixtures of these.Preference is given to 1,5-hexadiene, 5-ethylidenenorbornene anddicyclopentadiene. The diene content is preferably from 0.5 to 50% byweight, in particular from 2 to 20% by weight and particularlypreferably from 3 to 15% by weight, based on the total weight of theolefin polymer.

[0128] Examples of suitable esters f₃) are methyl, ethyl, propyl,n-butyl, isobutyl, 2-ethylhexyl, octyl and decyl acrylates and thecorresponding methacrylates. Among these preference is given to methyl,ethyl, propyl, n-butyl and 2-ethylhexyl acrylate and methacrylate.

[0129] Instead of the esters f₃), or in addition to these, the olefinpolymers may also comprise acid-functional and/or latentlyacid-functional monomers derived from ethylenically unsaturated mono- ordicarboxylic acids f₄).

[0130] Examples of monomers f₄) are acrylic acid, methacrylic acid,tertiary alkyl esters of these acids, in particular tert-butyl acrylate,and dicarboxylic acids, such as maleic acid and fumaric acid, andderivatives of these acids, and also their half esters.

[0131] For the purposes of the invention, latently acid-functionalmonomers are those compounds which under the conditions of thepolymerization or during incorporation of the olefin polymers into themolding compositions form free acid groups. Examples of these areanhydrides of dicarboxylic acids having from 2 to 20 carbon atoms, inparticular maleic anhydride, and tertiary C₁-C₁₂-alkyl esters of theabovementioned acids, in particular tert-butyl acrylate and tert-butylmethacrylate.

[0132] Ethylenically unsaturated dicarboxylic acids and anhydrides f₄)have the following formulae IV and V:

R²C(COOR³)═C(COOR⁴)R⁵  (IV)

[0133] where R², R³, R⁴ and R⁵, independently of one another, are H orC₁-C₆-alkyl.

[0134] Monomers f₅) containing epoxy groups have the following formulaeVI and VII

[0135] where R⁶, R⁷, R⁸ and R⁹, independently of one another, are H orC₁-C₆-alkyl, m is an integer from 0 to 20, and p is an integer from 0 to10.

[0136] R² to R⁹ are preferably hydrogen, m is preferably 0 or 1 and p ispreferably 1.

[0137] Preferred compounds f₄) and, respectively, f₅) are maleic acid,fumaric acid and maleic anhydride and, respectively, alkenyl glycidylethers and vinyl glycidyl ether.

[0138] Particularly preferred compounds of the formulae IV and V and,respectively, VI and VII are maleic acid and maleic anhydride and,respectively, acrylates and/or methacrylates both of which contain epoxygroups, in particular glycidyl acrylate and glycidyl methacrylate.

[0139] Particularly preferred olefin polymers are those made from from50 to 98.9% by weight, in particular from 60 to 94.85% by weight, ofethylene, and from 1 to 50% by weight, in particular from 5 to 40% byweight, of an ester of acrylic or methacrylic acid, and from 0.1 to20.0% by weight, in particular from 0.15 to 15% by weight, of glycidylacrylate and/or glycidyl methacrylate, acrylic acid and/or maleicanhydride.

[0140] Particularly suitable functionalized rubbers F are

[0141] ethylene-methyl methacrylate-glycidyl methacrylate polymers,

[0142] ethylene-methyl acrylate-glycidyl methacrylate polymers,

[0143] ethylene-methyl acrylate-glycidyl acrylate polymers and

[0144] ethylene-methyl methacrylate-glycidyl acrylate polymers.

[0145] Examples of other monomers f₆) are vinyl esters and vinyl ethers.

[0146] The polymers described above may be prepared by processes knownper se, preferably by random copolymerization at high pressure andelevated temperature.

[0147] The melt index of the copolymers is generally from 1 to 80 g/l 0min (measured at 190° C. and 2.16 kg load).

[0148] Core-shell graft rubbers are another group of suitable rubbers.These are graft rubbers prepared in emulsion and composed of at leastone hard and one soft constituent. Usually, a hard constituent is apolymer with a glass transition temperature of at least 25° C., and asoft constituent is a polymer with a glass transition temperature of notmore than 0° C. These products have a structure made from a core andfrom at least one shell, and the structure is a result of the sequenceof addition of the monomers. The soft constituents generally derive frombutadiene, isoprene, alkyl acrylates, alkyl methacrylates or siloxanesand, if desired, other comonomers. Suitable siloxane cores may beprepared, for example, starting from cyclic oligomericoctamethyltetrasiloxane or from tetravinyltetramethyltetrasiloxane.These may, for example, be reacted withγ-mercaptopropylmethyldimethoxysilane in a ring-opening cationicpolymerization, preferably in the presence of sulfonic acids, to givethe soft siloxane cores. The siloxanes may also be crosslinked by, forexample, carrying out the polymerization in the presence of silaneshaving hydrolyzable groups, such as halo or alkoxy, for exampletetraethoxysilane, methyltrimethoxysilane or phenyltrimethoxysilane.Examples of suitable comonomers for this are styrene, acrylonitrile andcrosslinking or grafting monomers having more than one polymerizabledouble bond, for example diallyl phthalate, divinylbenzene, butanedioldiacrylate and triallyl (iso)cyanurate. The hard constituents generallyderive from styrene, α-methylstyrene or from copolymers of these, andpreferred comonomers here are acrylonitrile, methacrylonitrile andmethyl methacrylate.

[0149] Preferred core-shell graft rubbers comprise a soft core and ahard shell or a hard core, a first soft shell and at least one furtherhard shell. The incorporation of functional groups here, such ascarbonyl, carboxylic acid, anhydride, amide, imide, carboxylic ester,amino, hydroxyl, epoxy, oxazoline, urethane, urea, lactam or halobenzyl,preferably takes place by adding suitably functionalized monomers duringthe polymerization of the final shell. Examples of suitablefunctionalized monomers are maleic acid, maleic anhydride, half estersor diesters, or maleic acid, tert-butyl (meth)acrylate, acrylic acid,glycidyl (meth)acrylate and vinyloxazoline. The proportion of monomerswith functional groups is generally from 0.1 to 25% by weight,preferably from 0.25 to 15% by weight, based on the total weight of thecore-shell graft rubber. The weight ratio of soft to hard constituentsis generally from 1:9 to 9:1, preferably from 3:7 to 8:2.

[0150] Rubbers of this type are known per se and are described, forexample, in EP-A-0 208 187. One way of incorporating oxazine groups forfunctionalization is as in EP-A-0 791 606.

[0151] Thermoplastic polyester elastomers are another group of suitableimpact modifiers. For the purposes of the invention, polyesterelastomers are segmented copolyetheresters which comprise long-chainsegments generally deriving from poly(alkylene) ether glycols andshort-chain segments deriving from low-molecular-weight diols anddicarboxylic acids. Products of this type are known per se and aredescribed in the literature, for example in U.S. Pat. No. 3,651,014.Corresponding products are also available commercially as Hytrel® (DuPont), Arnitel® (Akzo) and Pelprene® (Toyobo Co. Ltd.).

[0152] It is also, of course, possible to use mixtures of variousrubbers.

[0153] Component G

[0154] The amount of component G present in the molding compositions ofthe invention is from 0 to 40% by weight, preferably from 0 to 20% byweight, with preference from 0 to 10% by weight, and in the case ofstabilizers particularly from 0 to 1% by weight.

[0155] Component G comprises the usual additives and processing aids forpolyamide blends. Examples which should be mentioned of additives ofthis type are: dyes, pigments, colorants, antistats, antioxidants,stabilizers to improve heat resistance, to increase light resistance, orto raise hydrolysis resistance or chemicals resistance, agents toinhibit decomposition caused by heat, and in particular the lubricantsuseful for producing moldings. These other additives may be metered inat any stage of the preparation process, but preferably at an earlystage, so that the stabilizing effects (or other specific effects) ofthe additive are utilized at an early juncture. In polyphenyl etherblends use may particularly be made of flame retardants, for example.Examples of suitable flame retardants are polyhalobiphenyl,polyhalodiphenyl ether, polyhalophthalic acid, and derivatives thereof,and polyhalooligo- and -polycarbonates, the corresponding brominecompounds being particularly effective.

[0156] Examples of these are polymers of 2,6,2′,6′-tetrabromobisphenolA, of tetrabromophthalic acid, of 2,6-dibromophenol and of2,4,6-tribromophenol, and derivatives of these. Preferred flameretardant is elemental phosphorus. The elemental phosphorus maygenerally be coated or phlegmatized, for example with polyurethanes oramino plastics.

[0157] Concentrates of red phosphorus, for example in a polyamide, inelastomers or in polyolefins, are also suitable. Particular preferenceis given to combinations of elemental phosphorus with1,2,3,4,7,8,9,10,13,13,14,14-dodecachloro-1,4,4a,5,6,6a,7,10,10a,11,12,12a-dodecahydro-1,4:7,10-dimethanodibenzo(a,e)cyclooctane(Dechlorane®Plus, Occidental Chemical Corp.), and, where appropriate,with a synergist, such as antimony trioxide. Phosphorus compounds, suchas organic phosphates, phosphonates, phosphinates, phosphine oxides,phosphines or phosphites, are also preferred. Examples which should bementioned are triphenylphosphine oxide and triphenyl phosphate. Thismaterial may be used alone or mixed with hexabromobenzene or with achlorinated biphenyl and, if desired, antimony oxide. Typical preferredphosphorus compounds which may be used according to the presentinvention are those of the formula

[0158] where Q are identical or different hydrocarbon radicals, such asalkyl, cycloalkyl, aryl, alkyl-substituted aryl or aryl-substitutedalkyl, or halogen, hydrogen, or combinations of these, with the provisothat at least one of the radicals Q is aryl.

[0159] Examples of suitable phosphates of this type are the following:

[0160] phenyl bisdodecyl phosphate, phenyl bisneopentyl phosphate,phenyl ethyl hydrogenphosphate, phenyl bis(3,5,5-trimethylhexyl)phosphate, ethyl diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate, phenylmethyl hydrogenphosphate, di(dodecyl) p-tolyl phosphate, tricresylphosphate, triphenyl phosphate, dibutyl phenyl phosphate and diphenylhydrogenphosphate. Preferred phosphates are those where each Q is aryl.The most preferred phosphate is triphenyl phosphate. Preference is alsogiven to the combination of triphenyl phosphate with hexabromobenzeneand antimony trioxide.

[0161] Other compounds suitable as flame retardants are those whichcontain phosphorus-nitrogen bonds, for example phosphonitrile chloride,phosphoric ester amides, phosphoric ester amines, phosphoramides,phosphonamides, tris(aziridinyl)phosphine oxide andtetrakis(hydroxymethyl)phosphonium chloride. Most of the flameretardants are commercially available.

[0162] Other suitable flame retardants are hydroxides of magnesium,where appropriate coated with silane compounds.

[0163] Other halogen-containing flame retardants are tetrabromobenzene,hexachlorobenzene and hexabromobenzene, and halogenated polystyrenes andpolyphenylene ethers.

[0164] The halogenated phthalimides described in DE-A-19 46 924 may alsobe used. Of these, N,N′-ethylenebistetrabromophthalimide has gainedparticular importance.

[0165] Examples of other usual additives are stabilizers and oxidationinhibitors, agents to inhibit decomposition caused by heat ordecomposition caused by ultraviolet light, lubricants, mold-releaseagents, dyes, pigments and plasticizers.

[0166] Examples of oxidation retarders and heat stabilizers which may beadded to the molding compositions of the invention are halides of metalsof group I of the Periodic Table, e.g. sodium halides, potassium halidesand lithium halides, where appropriate in combination with copper(I)halides, e.g. with chlorides, bromides or iodides. Zinc fluoride andzinc chloride may also be used. It is also possible to use stericallyhindered phenols, hydroquinones, substituted members of this group, ormixtures of these compounds, preferably in concentrations of up to 1% byweight, based on the weight of the mixture.

[0167] Examples of UV stabilizers are various substituted resorcinols,salicylates, benzotriazoles and benzophenones, usually used in amountsof up to 23% by weight.

[0168] The lubricants and mold-release agents, generally used in amountsof up to 1% by weight of the molding composition, are stearic acid,stearyl alcohol, alkyl stearates and stearamides, and also esters ofpentaerythritol with long-chain fatty acids.

[0169] The additives also include stabilizers which inhibit thedecomposition of the red phosphorus in the presence of moisture andatmospheric oxygen. Examples of these which should be mentioned arecompounds of cadmium, of zinc, of aluminum, of silver, of iron, ofcopper, of antimony, of tin, of magnesium, of manganese, of vanadium, ofboron and of titanium. Examples of particularly suitable compounds areoxides of the metals mentioned, and also carbonates and oxycarbonates,hydroxides, and also salts of organic or of inorganic acids, for exampleacetates or phosphates or hydrogenphosphates, or sulfates.

[0170] A preferred stabilizer which may be present in the moldingcompositions of the invention is at least one phosphorus-containinginorganic acid or derivatives thereof, in amounts of up to 1000 ppm,preferably from 30 to 200 ppm, and particularly from 50 to 130 ppm,based on the phosphorus content of the compounds.

[0171] Preferred acids are hypophosphorous acid, phosphorous acid andphosphoric acid, and also salts thereof with alkali metals, particularlypreferably sodium or potassium. Among organic derivatives of these acidspreference is given to ester derivatives of abovementioned acids withfatty acids, the fatty acids having from 12 to 44 carbon atoms,preferably from 22 to 40 carbon atoms. Examples of these which should bementioned are stearic acid, behenic acid, palmitic acid and montanicacid.

[0172] Nucleating agents which may be used are sodium phenylphosphinate,aluminum oxide, silicon dioxide, nylon-2,2, and also preferably talc.

[0173] Lubricants and mold-release agents, usually used in amounts of upto 1% by weight, are preferably long-chain fatty acids (such as stearicacid or behenic acid), their salts (such as Ca stearate or Zn stearate)or ester derivatives (such as stearyl stearate or pentaerythritoltetrastearate), or else amide derivatives (such asethylenebisstearylamide).

[0174] Examples which should be mentioned of plasticizers are dioctylphthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils,N-(n-butyl)benzenesulfonamide, and o- and p-tolylethylsulfonamide.

[0175] Pigments and dyes are generally present in amounts of up to 4% byweight, preferably from 0.5 to 3.5% by weight, and particularly from 0.5to 3% by weight.

[0176] The pigments for coloration of thermoplastics are well known, seefor example R. Gächter and H. Müller, Taschenbuch derKunststoffadditive, Carl Hanser Verlag, 1983, pp. 494-510. A firstpreferred group of pigments is that of white pigments, such as zincoxide, white lead (2PbCO₃.Pb(OH)₂), lithopones, antimony white andtitanium dioxide. Of the two most common crystal forms of titaniumdioxide (rutile and anatase) it is the rutile form in particular whichis used for white coloration of the molding compositions of theinvention.

[0177] Black pigments which may be used according to the invention areiron oxide black (Fe₃O₄), spinel black (Cu(Cr,Fe)₂O₄), manganese black(a mixture of manganese dioxide, silica and iron oxide), cobalt blackand antimony black, and particularly preferably carbon black, usuallyused in the form of furnace black or gas black (see in this connectionG. Benzing, Pigmente für Anstrichmittel, Expert-Verlag (1988), pp.78ff.).

[0178] Inorganic color pigments, such as chromium oxide green, ororganic color pigments, such as azo pigments and phthalocyanines, may,of course, be used according to the invention to achieve particularshades of color. Pigments of this type are widely availablecommercially.

[0179] It can also be advantageous to use the pigments or dyes mentionedin mixtures, such as carbon black with copper phthalocyanines, thismethod generally making it easier to disperse the color in thethermoplastic.

[0180] Component H

[0181] As component H, use is made of from 100 ppm to 0.5% by weight,preferably from 0.001 to 0.1% by weight, particularly from 0.005 to0.02% by weight, of copper bromide and/or copper iodide, based oncomponents A to G.

[0182] The molding compositions of the invention may be prepared byknown processes, by mixing components A, C, D, E, H and, whereappropriate, B, F and G.

[0183] The sequence of mixing the components may be as desired. Forexample, the molding compositions of the invention may be prepared byextrusion, one way being to mix the starting components in conventionalmixing equipment, such as screw extruders, preferably twin-screwextruders, Brabender mixers or Banburry mixers, or in kneaders, followedby extrusion. The extrudate is cooled and comminuted. The sequence ofmixing the components may be varied, for example two or, whereappropriate, three components may be premixed. However, it is alsopossible for all of the components to be mixed together.

[0184] To obtain very homogeneous mixing, intensive mixing isadvantageous. For this, the average mixing times required are generallyfrom 0.2 to 30 minutes at from 280 to 370° C., preferably from 290 to360° C. The extrudate is generally cooled and comminuted.

[0185] The molding compositions of the invention have very good heatresistance up to 150° C., and also improved flowability and impactstrength.

[0186] The examples below further illustrate the invention.

EXAMPLES

[0187] The viscosity number of the polyaryl ethers is determined in 1%strength solution in N-methylpyrrolidone at 25° C. The proportion ofunits having acid groups in the copolyaryl ethers C) was determined by¹H NMR spectroscopy, as in I. W. Parsons et al., Polymer 34, 2836(1993).

[0188] The OH end group concentration is determined by potentiometrictitration in dimethylformamide.

[0189] The viscosity of the polyamides is determined to DIN 53 727 on0.5% strength by weight solutions in 96% strength by weight sulfuricacid.

[0190] Preparation and Testing of the Molding Compositions

[0191] The heat resistance of the specimens was determined via theirVicat softening point. The Vicat softening point was determined to DIN53 460 with a force of 49.05 N and a temperature rise of 50 K per hour,using standard small specimens.

[0192] The impact strength of the products was determined on ISOspecimens to ISO 179 leU. Stiffness (modulus of elasticity) wasdetermined to DIN 53 457, and tensile strength and elongation at breakto DIN 53 455.

[0193] Flowability was determined to DIN 53 735 at 300° C. with 10 kgload.

[0194] To characterize heat resistance, tensile specimens were aged at180° C. for a period of 1000 h. After 100, 500 and 1000 h test specimenswere removed and tensile-tested. In each case, the level of ultimatetensile strength is listed in Table 1, based on the initial level (in

[0195] Component A1

[0196] The polyarylene ether sulfone A1 used was Ultrason® E 2010(commercial product of BASF AG). This product is characterized by aviscosity number of 54 ml/g, measured in 1% strength NMP solution at 25°C.

[0197] Component B1

[0198] Under an atmosphere of nitrogen, 5.167 kg of dichlorodiphenylsulfone, 4.3905 kg of dihydroxydiphenyl sulfone and 128.85 g of4,4′-dihydroxyvaleric acid were dissolved in 29 kg ofN-methylpyrrolidone and mixed with 2.820 kg of anhydrous potassiumcarbonate. The reaction mixture was firstly heated for 1 h at 180° C. ata pressure of 300 mbar with continuous distilling-off of the water ofreaction and N-methylpyrrolidone, and then reacted further for 6 h at190° C. After adding 40 kg of N-methylpyrrolidone, the inorganicconstituents were filtered off. Basic groups were neutralized by adding300 ml of glacial acetic acid, and the polymer was then isolated byprecipitation in water. After three extractions with water, the productwas dried in vacuo at 140° C. to give a white powder. The proportion ofunits with acid groups was determined by ¹H NMR as 1.4 mol %, and theviscosity number of the product was 32.7 ml/g.

[0199] Component B2

[0200] Under an atmosphere of nitrogen, 5.740 kg of dichlorodiphenylsulfone and 5.003 kg of dihydroxydiphenyl sulfone were dissolved in 29kg of N-methylpyrrolidone and mixed with 2.820 kg of anhydrous potassiumcarbonate. The reaction mixture was firstly heated for 1 h at 180° C. ata pressure of 300 mbar with continuous distilling-off of the water ofreaction and N-methylpyrrolidone, and then reacted further for 6 h at190° C. After adding 40 kg of N-methylpyrrolidone, the inorganicconstituents were filtered off. Basic groups were neutralized by adding300 ml of glacial acetic acid, and the polymer was then isolated byprecipitation in water. After three extractions with water, the productwas dried in vacuo at 140° C. to give a white powder.

[0201] The proportion of units with OH end groups was determined by as0.14% by weight, and the viscosity number of the product was 56.2 ml/g.

[0202] Component C1

[0203] As polyamide C1, use was made of a partly aromatic copolyamidecondensed from 55 parts by weight of terephthalic acid, 35 parts byweight of ε-caprolactam and 38.5 parts of hexamethylenediamine, andcharacterized by a viscosity number of 210 ml/g (measured at 0.5%strength by weight in 96% strength sulfuric acid). This product isfurther characterized by a glass transition point at 110° C. and by amelting peak at 289° C.

[0204] Component C2

[0205] As polyamide C2, use was made of a nylon-6 obtained fromε-caprolactam and having a viscosity number of 250 ml/g (measured at0.5% strength by weight in 96% strength sulfuric acid), e.g. Ultramid®B4.

[0206] Component D1

[0207] Epoxy resin with a softening point of 150° C. and with an epoxyvalue of 0.37 eq/kg, e.g. Araldit® 6609 from Ciba.

[0208] Component E1

[0209] Chopped glass fibers with polyurethane size, fiber diameter 10μm.

[0210] Component H

[0211] CuI was used as stabilizer.

[0212] The components were mixed in a twin-screw extruder at a melttemperature of from 300 to 350° C. The melt was passed through a waterbath and pelletized.

[0213] The molding compositions comprising the polyether sulfone wereprocessed at 340° C. The mold temperature was always 100° C.

[0214] The results of the tests are listed in Table 1 below. TABLE 1Molding composition 1c 1 2 2c 3c 3 4 A1 49 48 46 49 42 46 46 B1 — — — —7 2 — B2 — — 2 — — — 2 C1 20.99 20.99 20.99 — — — — C2 — — — 20.99 20.9920.99 20.99 D1 — 1 1 — — 1 1 E1 30 30 30 30 30 30 30 H 0.01 0.01 0.010.01 0.01 0.01 0.01 Vicat B[° C.] 206 205 205 202 203 203 203an[kJ/m^(2]) 51 59 62 52 65 69 67 Modulus of 11.7 11.7 11.6 11.7 11.811.7 11.8 elasticity [kN/mm²] MVI[ml/10′] 24 34 36 32 27 41 39 Ultimatetensile strength [%] After 100 h 96 94 95 97 95 96 96 After 250 h 87 8689 91 91 92 92 After 1000 h 83 82 83 90 89 91 91

[0215] The thermoplastic molding compositions of the invention have verygood heat resistance, and also improved flowability and impact strength.

We claim:
 1. A thermoplastic molding composition comprising componentsA, C, D, E and, where appropriate, B, F and G, the total weight of whichis 100% by weight, and also component H: a) as component A, from 5 to94.8% by weight of at least one polyaryl ether sulfone, b) as componentB, from 1 to 10% by weight of at least one functionalized polyaryl ethersulfone, c) as component C, from 5 to 94.8% by weight of at least onepolyamide, d) as component D, from 0.1 to 10% by weight of at least oneepoxy resin, e) as component E, from 0.1 to 60% by weight of fibrous orparticulate fillers or a mixture of these, f) as component F, from 0 to40% by weight of impact-modifying rubbers which have functional groups,g) as component G, from 0 to 40% by weight of other conventionaladditives and processing aids, h) as component H, from 100 ppm to 0.5%by weight, based on the amounts of components A to G, of copper bromideand/or copper iodide.
 2. A molding composition as claimed in claim 1,wherein the structure of component A has repeat units of the formula I

where t and q, independently of one another, are 0, 1, 2 or 3, each ofQ, T and Z, independently of one another, is a chemical bond or a groupselected from the class consisting of —O—, —S—, —SO₂—, S═O, C═O, —N═N—,—R^(a)C═CR^(b)— and —CR^(c)R^(d)—, where each of R^(a) and R^(b),independently of one another, is hydrogen or C₁-C₁₂-alkyl and each ofR^(c) and R^(d), independently of one another, is hydrogen orC₁-C₁₂-alkyl, C₁-C₁₂-alkoxy or C₆-C₁₈-aryl, where R^(c) and R^(d) may,if desired, independently of one another have fluorine and/or chlorinesubstituents or, together with the carbon atom to which they are bonded,may form a C₃-C₁₂-cycloalkyl group, which may be unsubstituted orsubstituted by one or more C₁-C₆-alkyl groups, with the proviso that atleast one of the groups T, Q and Z is —SO₂— or C═O and if t and q are 0,Z is —SO₂—, and Ar and Ar¹, independently of one another, areC₆-C₁₈-arylene, unsubstituted or substituted by C₁-C₁₂-alkyl,C₆-C₁₈-aryl, C₁-C₁₂-alkoxy or halogen.
 3. A molding composition asclaimed in claim 1 or 2, wherein carbon fibers, potassium titanatewhiskers, aramid fibers or glass fibers are used as component E.
 4. Amolding composition as claimed in any of claims 1 to 3, whereincomponent D has the following formula II D:

where n=from 2 to 50, and R^(1′) is hydrogen or C₁-C₁₆-alkyl.
 5. Aprocess for preparing molding compositions as claimed in any of claims 1to 4 by mixing components A, C, D, E, H and, where appropriate, B, F andG.
 6. The use of molding compositions as claimed in any of claims 1 to 4for producing fibers, films or moldings.
 7. A fiber, a film or a moldingmade from a molding composition as claimed in any of claims 1 to 4.